Doping mechanisms and electrical properties of bismuth tantalate fluorites

Phase-pure bismuth tantalate fluorites were successfully prepared via conventional solid-state method at 900 °C in 24–48 h. The subsolidus solution was proposed with the general formula of Bi_3+x Ta_1?x O_7?x (0 ≤ x ≤ 0.184), wherein the formation mechanism involved a one-to-one replacement of Ta⁵⁺ cation by Bi³⁺ cation within ~4.6 mol% difference. These samples crystallised in a cubic symmetry, space group Fm-3 m with lattice constants, a = b = c in the range 5.4477(± 0.0037)–5.4580(± 0.0039) Å. A slight increment in the unit cell was discernible with increasing Bi₂O₃ content, and this may attribute to the incorporation of relatively larger Bi³⁺ cation in the host structure. The linear correlation between lattice parameter and composition variable showed that the Vegard’s law was obeyed. Both TGA and DTA analyses showed Bi_3+x Ta_1?x O_7?x samples to be thermally stable as neither phase transition nor weight loss was observed within ~28–1000 °C. The AC impedance study of Bi₃TaO₇ samples was performed over the frequency range 5–13 MHz. At intermediate temperatures, ~350–850 °C, Bi_3+x Ta_1?x O_7?x solid solution was a modest oxide ion conductor with conductivity, ~10^?6–10^?3 S cm^?1; the activation energy was in the range 0.98–1.08 eV.     

Phase equilibria and crystal structures of solid solutions in the system LaCoO<Subscript>3−δ</Subscript>-SrCoO<Subscript>2.5±δ</Subscript>-SrFeO<Subscript>3−δ</Subscript>-LaFeO<Subscript>3−δ</Subscript>

The composition region and structure of La_1?x Sr _x Co_1?y Fe _y O_3?δ solid solutions are determined by x-ray powder diffraction using the Rietveld profile analysis method. The solid solutions based on lanthanum cobaltite, LaCoO_3?δ, have a rhombohedrally distorted perovskite-like structure (sp. gr. R \(\bar 3\) c), and those based on lanthanum ferrite, LaFeO_3?δ, have an orthorhombically distorted structure (sp. gr. Pbnm). The rhombohedral distortion decreases with increasing strontium content, and the solid solutions with x ≥ 0.5 have an ideal cubic structure (sp. gr. Pm3m). The composition dependences of lattice parameters for the La_1?x Sr _x Co_1?y Fe _y O_3?δ solid solutions are presented, and the 1100°C isotherm of the LaCoO_3?δ-SrCoO_2.5±δ-SrFeO_3?δ-LaFeO_3?δ system in air is constructed.     

Electrical conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions

New solid solutions, Bi_2?x?y Tm _x Nb _y O_3+δ, with tetragonal and cubic structures have been synthesized in the Bi₂O₃-Tm₂O₃-Nb₂O₅ system, and their electrical conductivity has been measured at temperatures from 670 to 1020 K. The 1020-K conductivity of the tetragonal solid solution Bi_1.8Tm_0.15Nb_0.05O_3+δ is comparable to that of Bi_1.75Tm_0.25O₃, the best conductor in the Bi₂O₃-Tm₂O₃ system.     

Effects on dielectric and magnetic properties of Cr-doped Bi<Subscript>0.9</Subscript>Ba<Subscript>0.1</Subscript>Fe<Subscript>1−x</Subscript>Cr<Subscript>x</Subscript>O<Subscript>3</Subscript> ceramic

In this paper, Cr-doped Bi_0.9Ba_0.1Fe_1?xCr_xO₃ (x = 0.00, 0.05, 0.10, 0.15, 0.20) ceramic materials were prepared by traditional state solid synthesized method, and the effects of Cr³⁺ ion on magnetic and dielectric properties were investigated. All samples showed BiFeO₃ phase formation were successful synthesized. The SEM images showed the shape of samples changed from regular to irregular shape. With increasing of Cr²⁺ ions, Saturation magnetization (M _s) increased from 5.24 to 8.6 emu/g, and then decreased to 7.31 emu/g, and coercivity (H _c) increased from 110.66 to 256.49 Oe. All the samples showed high dielectric constants at low frequency and the values of dielectric constants decreased slightly with frequency increasing. Delectric loss (tanδ) values kept a steady in a wide range frequency of 10–600 MHz. They ranged in tanδ from 0.01 to 0.07, which was a low dielectric loss in Bi_0.9Ba_0.1Fe_1?xCr_xO₃ ceramics.     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Electrical and Dielectric Characterization of Bi–La Ion-Substituted Barium Hexaferrites

BaLa _x Bi _x Fe_12?2xO₁₉ (0.0 ≤ x ≤ 0.5) hexaferrites were produced by solid-state synthesis route, and the effect of Bi³⁺ and La³⁺ substitutions on electrical and dielectric properties of barium hexaferrite material were investigated. It is noticed that ac conductivity of barium (BaM) increases slightly with ionic substitutions of both La³⁺ and Bi³⁺ and then decreases. Ac conductivity is increased with increasing frequency at lower temperatures then remains constant for higher temperatures. This type of conductivity attitude could be originated from the indication of both electronics and polaron hopping mechanisms. The dielectric properties of BaLa _x Bi _x Fe_12?2xO₁₉ (0.0 ≤ x ≤ 0.5) hexaferrites represent a very interesting tunability as functions of frequency, temperature, and Bi³⁺ and La³⁺ ions.     

Structural relaxation and electrical conductivity of molybdovanadate glass

⁵⁷Fe Mössbauer spectrum of conductive barium iron vanadate glass with a composition of 20BaO·10Fe₂O₃·70V₂O₅ (in mol%) showed paramagnetic doublet peak due to distorted Fe^IIIO₄ tetrahedra with isomer shift (δ) value of 0.37 (±?0.01) mm s^?1. Mössbauer spectra of 20BaO·10Fe₂O₃·xMoO₃·(70???x)V₂O₅ glasses (x?=?20–50) showed paramagnetic doublet peaks due to distorted Fe^IIIO₆ octahedra with δ’s of 0.40–0.41 (±?0.01) mm s^?1. These results evidently show a composition-dependent change of the 3D-skeleton structure from “vanadate glass” phase, composed of distorted VO₄ tetrahedra and VO₅ pyramids, to “molybdate glass” composed of distorted MoO₆ octahedra. After isothermal annealing at 500 °C for 60 min, Mössbauer spectra also showed a marked decrease in the quadrupole splitting (Δ) of Fe^III from 0.70 to 0.77 to 0.58–0.62 (±?0.02) mm s^?1, which proved “structural relaxation” of distorted VO₄ tetrahedra which were randomly connected to FeO₄, VO₅, MoO₆, FeO₆ and MoO₄ units by sharing corner oxygen atoms or edges. DC-conductivity (σ) of barium iron vanadate glass (x?=?0) measured at room temperature was 3.2?×?10^?6 S cm^?1, which increased to 3.4?×?10^?1 S cm^?1 after the annealing at 500 °C for 60 min. The σ’s of as-cast molybdovanadate glasses with x’s of 20–50 were ca. 1.1?×?10^?7 or 1.2?×?10^?7S cm^?1, which increased to 2.1?×?10^?2 (x?=?20), 6.7?×?10^?3 (x?=?35) and 1.9?×?10^?4 S cm^?1 (x?=?50) after the annealing at 500 °C for 60 min. It was concluded that the structural relaxation of distorted VO₄ tetrahedra was directly related to the marked increase in the σ, as generally observed in several vanadate glasses.     

Stability region of Gd<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3 ± δ</Subscript> solid solutions in air

The solid-solution range of Gd_{2 ? x} Mn _x O_{3 ± δ} has been determined using X-ray diffraction analysis of samples with 0.90 ≤ x ≤ 1.20 (Δx = 0.02) prepared from oxide mixtures by solid-state reactions in air between 900 and 1400°C. The results have been used to construct a partial phase diagram of the Gd-Mn-O system in air. It is shown that gadolinium manganite with the perfect metal stoichiometry, GdMnO_{3 ± δ}, does not exist. The material of this composition in air consists of two phases: a Gd_{2 ? x} Mn _x O_{3 ± δ} solid solution with an orthorhombic perovskite-like structure and the binary oxide Gd₂O₃. The solid solution extends to the composition Gd_0.96Mn_1.04O_{3 ± δ}. Over the entire temperature range studied, gadolinium oxide does not dissolve in Gd_0.96Mn_1.04O_{3 ± δ}. Mn₃O₄ exhibits significant solubility in Gd_{2 ? x} Mn _x O_{3 ± δ}. In particular, Gd_0.86Mn_1.14 O_{3 ± δ} is single-phase by X-ray diffraction in the temperature range 1185–1400°C. Below 1185°C, Gd_{2 ? x} Mn _x O_{3 ± δ} is in equilibrium with another gadolinium manganite, GdMn₂O₅. With decreasing synthesis temperature, the GdMn₂O₅ solubility in Gd_{2 ? x} Mn _x O_{3 ± δ} drops precipitously. At 900°C, the only single-phase sample was Gd_0.96Mn_1.04O_{3 ± δ}.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Influence of Oxygen on the Tribomechanical Properties of Single Crystals of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−<Emphasis Type="Italic">δ</Emphasis></Subscript>

This paper reports a study on the mechanical and tribological properties of ab- and a (b) c?planes of YBa₂Cu₃O_7?δ single crystals. The single crystals were grown using a CuO-BaO self-flux method. The oxygenation effect on the mechanical and tribological properties of ab- and a (b) c?planes is reported. For the ab- plane, the hardness and elastic modulus were around 6 and 50 GPa, respectively. In this case, significant differences were not observed among the hardness and elastic modulus at different oxygenation states. However, the hardness and elastic modulus for as-grown and oxygenated YBa₂Cu₃O_7?δ single crystals were different from that of the a (b) c?plane, and were observed to be slightly higher for the as-grown than for the oxygenated samples. For as-grown and oxygenated samples, we observed hardness values around 4.7 and 2.0 GPa, respectively. Regarding the elastic modulus, the values were 75 and 40 GPa, respectively. The indentation fracture toughness values on the ab- plane for the as-grown and oxygenated YBa₂Cu₃O_7?δ single crystal were 3.7 ± 1.2 and 2.9 ± 1.2 MPa m^1/2, respectively. For the ab- plane, the scratch resistance of the as-grown sample was higher than that of the oxygenated sample and the scratches under load were deeper for the oxygenated sample. As regards the a (b) c?plane, the scar features were seemingly constant through all the scratch lengths and the scratches under load were deeper and larger for the oxygenated than that for the as-grown sample.     

Effect of Boron Substitution for Bi on Superconductivity of the Bi-2212 Phase in the Bi-Sr-Ca-Cu-O System

Possibility of boron substitution for Bi and the substitution effect on superconductivity is investigated for the Bi-2212 phase of Bi-Sr-Ca-Cu-O. From X-ray diffraction study, it is found that samples in the (Bi_2?x B _x )Sr₂CaCu₂O _z system are mainly of the single 2212 phase in a composition range of 0.0≤x≤0.6, and both of the lattice parameters a and c change with increasing x up to 0.6. From measurements of the magnetic susceptibility and the electrical resistivity, the superconducting transition temperature is found to increase up to 0.6 with increasing x. These results are considered to show that boron is substitutable for Bi up to x=0.6 in the (Bi_2?x B _x )Sr₂CaCu₂O _z system and that the boron substitution causes the number of hole-carriers to decrease in this system.     

Growth and properties of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript>-NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

Platelike Li_{1 ? x} Na _x Cu₂O₂ single crystals up to 2 × 10 × 10 mm in dimensions have been grown by slowly cooling (1 ? x)Li₂CO₃·xNa₂O₂·4CuO melts in alundum crucibles in air. Li_{1 ? x} Na _x Cu₂O₂ solid solutions in the LiCu₂O₂-NaCu₂O₂ system have been shown to exist in the composition range 0.78 < x < 1. The temperature stability ranges of NaCu₂O₂ and LiCu₂O₂ are 780–930 and 890–1050°C, respectively. The Mössbauer spectra and electrical conductivity of the crystals have been measured.     

Anisotropic Properties of Bi2Sr2−xLa<Emphasis Type="Italic">x</Emphasis>Cu1O6+δ Thin-Films Grown on Vicinal SrTiO3 Substrates

Epitaxial Bi₂Sr_2?xLa _x Cu₁O_6+δ thin films were grown on vicinal substrates by magnetron sputtering. The growth mode and the superconductivity of the thin films were studied. The films were deposited on 5–7° misoriented (100) SrTiO₃ (STO). The surface of misoriented substrate is tilted to the 〈111〉 azimuth. The topographies of the Bi-2201 films show strip-like shapes. The transmission electron microscopy (TEM) study revealed that the films grew with very good in-plane alignments which were comparable to those of single crystals. Both of the temperature dependence of the a- and c-axis resistivities were studied under magnetic fields. The corresponding anisotropic activation energies and upper critical magnetic fields were investigated.     

Lattice Energy Determination for Polycrystalline Oxide Ceramics and Single-Crystalline Counterparts

The compositional dependence of lattice energies for polycrystalline specimens of spinel ferrite systems, Zn _x Co_1?x Fe₂ O ₄ (x = 0.0–0.6); slowly cooled and quenched systems of CuAl _x Fe_2?x O ₄ (x = 0.0–0.6); high-energy ball milled mixed ferrite composition, Ni_0.5Zn_0.5Fe₂ O ₄ (0–9 h); garnet system, Y_3?x Fe_{5 + x} O ₁₂ (x = 0.0–0.5); manganite perovskite system, La_1?x Ca _x MnO₃ (x = 0.0–1.0); and superconducting systems, Bi_1.7?x Pb_0.3Al _x Sr₂Ca₂Cu₃ O ₁₀ (x = 0.0–0.3), Bi_1.7?x Pb_0.3Ga _x Sr₂CaCu₂ O ₈ (x = 0.0–0.3), and Bi₂Sr₂CaCu₂ O ₈+0??5 % Ag ⁺ addition has been evaluated, making use of mean sound velocity data and employing Kudriavtsev’s approach. It is found that for all the systems, lattice energy decreases, and it is explained based on the change in structural and microstructural parameters as a function of substitution. The lattice energies for single-crystalline counterparts have been computed using four different estimation models based on Kapustinskii method, molecular volume and X-ray density, connectivity indices, and chemical hardness. The observed difference between the two has been discussed in the light of grain and grain boundary contributions and presence of pores and microcracks in polycrystalline materials. A simple model suggested for lattice energy determination for complex oxide compositions based on the oxide additivity rule was found to be quite satisfactory.     

Performance enhancement in high-<Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript> ceramics through melting by Joule heating,infrared lamps,and laser radiation

We have analyzed experimental data on the effect of short-term melting followed by recrystallization on the microstructure and critical current density of YBa₂Cu₃O_{7 ? x} , Bi₂Sr₂CaCu₂O_{8 ? x} , and Bi₂Sr₂Ca₂Cu₃O_{10 ? x} high-T _c ceramics. The ceramics were melted using different heat sources: infrared lamps, laser radiation, and electric current. A significant increase in the critical current density of Bi₂Sr₂Ca₂Cu₃O_{10 ? x} ceramics (by a factor of 40 at 20 K and by a factor of 8 at 77 K) was achieved using cw CO₂ laser irradiation. Melting TiC-doped (0.1%) Bi₂Sr₂Ca₂Cu₃O_{10 ? x} ceramics with a CO₂ laser, followed by annealing, insured an even larger increase in critical current density: by a factor of 35 at 77 K. We have calculated the thickness of the molten layer produced by laser heating of high-T _c ceramics.     

High Pressure Synthesis of (La1−<Emphasis Type="Italic">x</Emphasis>Sr<Emphasis Type="Italic">x</Emphasis>)8O20, (0.25 ≤ x ≤ 0.65) with a Wide Solubility Range and High Cu-Valence

With an attempt to increase the Cu valence, we synthesized the (La_1?xSr _x )₈Cu₈O_20?δ (8-8-20 phase) compounds with large x using an O₂-HIP apparatus. By heat treatment in a high-pressure of oxygen gas (40 MPa), the 8-8-20 compounds were stabilized in the range of 0.25 ≤ x ≤ 0.65. Their crystal structures, characterized by x-ray Rietveld refinement and electron diffraction, are tetragonal, space group P4/mbm. The formal copper valence was found to increase with Sr concentration from 2.24 at x = 0.25 to 2.63 at x = 0.65, keeping the oxygen content constant around 20.0. Electrical resistivity and magnetic susceptibility showed only metallic behavior from room temperature down to 5 K with no sign of superconductivity.     

Synthesis and investigation of superconducting properties of heterosubstituted magnesium diborides

The properties of magnesium diborides with the composition Mg_{1 ? x} M _x B₂, where M = Al, Ga, In, and Tl, and Mg (B_{1 ? x} E _x ), where E = N, P, and Si (0.05 ≤ x ≤ 0.3), made by sintering of calculated amounts of boron, magnesium, and a substituent element or by a solid-phase exchange reaction of a corresponding halogenide of a metal with MgB₂ at 1070–1170 K are studied. Using RFA technique, it is shown that, from all employed heterosubstituents, only the atoms of aluminum, gallium, and silicon in the amount x ≤ 0.2 are incorporated into magnesium and boron sublatticies. Here, the temperature of the superconducting transition T _c = 39 ± 1K determined for pure magnesium diboride hardly changes.     

Phase Formation and Phase Transitions in Nonstoichiometric Sodium Bismuth Titanate Ceramics

We have studied the phase formation, microstructure, and dielectric and ferroelectric properties of (Na_0.5–xBi_0.5)TiO₃ and (Na_0.5Bi_{0.5 + x})TiO₃ nonstoichiometric ceramics with Na/Bi < 1 and x = 0–0.1. The grain size of the ceramics has been shown to decrease with increasing x. The temperature dependences of dielectric permittivity for the samples studied have anomalies near ~400 K and peaks at ~600 K, corresponding to ferroelectric phase transitions. The phase transitions near 400 K demonstrate relaxor behavior, indicative of the presence of polar regions in a nonpolar matrix, as supported by laser second harmonic generation measurements. In addition, the (Na_0.5Bi_{0.5 + x})TiO₃ samples with x > 0.05 have anomalies near 900 K, confirming the presence of Bi₄Ti₃O₁₂ as an impurity phase, which is accompanied by an increase in the spontaneous polarization of these samples.     

Enhanced magnetoelectric coupling in La-modified Bi<Subscript>5</Subscript>Co<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>Ti<Subscript>3</Subscript>O<Subscript>15</Subscript> multiferroic ceramics

Multiferroic properties of La-modified four-layered perovskite Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ (0 ≤ x ≤ 1) ceramics were investigated, by analyzing the magnetodielectric effect, magneto-polarization response and magnetoelectric conversion. X-ray diffraction indicated the formation of pure Aurivillius ceramics, and Raman spectroscopy revealed the Bi ions displacement and the crystal structure variation. The enhancement of ferromagnetic and ferroelectric properties was observed in Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ after La modification. The evidence for enhanced ME coupling was determined by magnetic field-induced marked variations in the dielectric constant and polarization. A maximum ME coefficient of 1.15 mV/cm·Oe was achieved in Bi_4.25La_0.75Fe_0.5Co_0.5Ti₃O₁₅ ceramic, which provides the possible promise for novel magnetoelectric device application.